Production of Fluorescent

Backbone Molecule
CME 431-1 Group 5
Bradley Siefker, RJ Schratz, David Devlin, Trevor Langton
April 21, 2017
Conclusions and Future Work
Project Overview
Project demands dictated producing 10,000 tons of 99.5 wt% pure tetraphenylethylene
(TPE) per year. Research on TPE markets indicate applications as a fluorescent biomarker
backbone, as well as potential applications in OLED TVs and solar panel coatings. The proposed
TPE production route is a series of three reactions. Chlorine gas (Cl2) and phosphorous
trichloride (PCl3) react to produce phosphorous pentachloride (PCl5). PCl5 reacts with an
equimolar flow of benzophenone form phosphorous oxychloride (POCl3) and
diphenyldichloromethane (DCPM). Following separation of POCl3, the DPCM interacts with a
nickle-glyme catalyst to form TPE. TPE is separated by centrifuge and magnetic separator to
achieve necessary product purity for sale.
The production route requires use of many toxic chemicals. Unintentional releases of any
reagents and intermediates pose long term and lasting effects to those in and outside the plant
and environment. Accidental release measures and third party waste management companies are
used to protect the health of all people and the environment from disaster. Despite the dangerous
nature of the chemicals and equipment demands, TPE production as proposed is financially
viable. Refinement of total product costs, necessary capital investments, and appropriate
environmental requirements will provide additional information before significant investments
are made into industrial TPE production.
Equipment Overview
To determine financial viability of the desired TPE purity at the specified production rate,
all major process equipment was sized and costed. Three reactors are required to convert
benzophenone, Cl2and PCl3 to the final TPE product. Three unique separation systems were
implemented to remove impurities from final product, recycle the expensive nickle-glyme
catalyst, and to separate out the POCl3 byproduct for sale. Heat transfer equipment was sized for
a packed distillation column condenser and reboiler, reactor heating and cooling systems, and
process stream cooling.
All three reactors in the proposed TPE production route were sized as continuous stirred
tank reactors (CSTR). Reactor volumes were calculated from ChemCad simulated solution
densities and literature residence times. The PCl5DPCM, and TPE reactors are 0.36, 11.0, and
0.30 m3 respectively. A cooling jacket is used to keep operating temperatures below 50 C and
remove 351 MJ/hr of heat from the exothermic PCl5 reaction. The DPCM reactor requires 930
MJ/hr of heating supplied via a fuel fired heater to maintain the endothermic reaction at 220 C.
Vapors evolved from this reaction are condensed with a shell and tube heat exchanger to remove
295 MJ/hr of heat. The endothermic TPE reaction is supplied 666 MJ/hr of heat from DPCM
exiting the distillation column before being fed into the reactor. To maintain necessary corrosion
resistances PCl5DPCM, and TPE reactors are constructed from Monel, Hastelloy C276, and
glass lined steel respectively.
Three separation systems are designed for TPE production. Mass flow rate and
volumetric flow rate were required for sizing of the magnetic separator and centrifugal separator.
The magnetic drum separator is 0.3048 m in diameter and is used to remove the nickle-glyme
catalyst and any trace metal impurities. The centrifugal separator has a bowl diameter of 0.48 m
and is used to effectively remove any trace DPCM to deliver TPE of a purity greater than 99.5%.
A packed distillation column sized filled with 6 mm glass Raschig rings are used to separate
POCl3 and DPCM. ChemCad analysis of the impact of reflux ratio on energy demands and
production rates determined a reflux ratio of 0.75 to achieve desired production rates. The
McCabe-Thiele method estimated 5 stages to achieve separation. The final column is 1 m tall
and 0.63 m in diameter constructed of Hastelloy C276. A concentric tube heat exchanger and a
shell and tube heat exchanger remove 308 MJ/hr of heat to cool and condense distillate vapors. A
fuel fire reboiler supplies the 440 MJ/hr to for the column reboiler.
All heat transfer equipment is constructed of Hastelloy C276 to ensure adequate
corrosion resistance. Heat transfer coefficients for the process fluid are calculated using Nusselt
and Donoughe equations. Heat demands, overall heat transfer coefficients and log mean
temperature differences are used to calculate the areas of all heat transfer equipment. Heat
transfer areas and selected pipe diameter are used to provide accurate costing of all heat transfer
equipment. The total cost of all major unit operations in the proposed TPE production route is
$2.73 million.
Economic Conclusions
The purchased equipment cost for all unit operations are determined using semi-log plots
which relate cost to capacity. Heuristics related purchased equipment cost to the capital costs
associated with the production of TPE. The fixed capital investment (FCI) is $11 million. At 20
percent of the FCI, the working capital (WC) is $2.2 million. The total capital investment (TCI)
of the process is $13.2 million. Of the fixed capital, all components except land were linearly
depreciated over 20 years for a yearly depreciation allowance of $541,000.
Total Product Cost (TPC), which is the sum of manufacturing costs, fixed charges and
general expenses, was found to be $30.25 million. Utility loads and labor are minor contributors
to the TPC, as they only account for 0.3 and 5 percent of the costs. Utility load cost is
concentrated in three unit operations: natural gas for the diphenyl-dichloromethane reactor,
electricity for the centrifuge and cooling water for the PCl5 reactor. The largest component of
TPC is the cost of raw materials, at approximately 60 percent of the TPC.
Revenues are generated by two products POCl3 and TPE. While POCl3 has an
established market value of $1.10 per kg, prices for TPE are unclear, as the product is still in the
introduction stage of its product cycle. If TPE is sold at a price of $2.79 per kg, the process
generates a discounted cash flow rate of return of 15%. This price less than 1% of current bulk
export pricing, which is $657 per kg. While unreasonable to suggest this pricing would be
maintained at 10,000 tons of production, the investment is attractive. It is unlikely the price will
fall below $2.79 per kg, therefore production of TPE as described should be explored further.
Future Work
Before implementation, numerous aspects of the proposed TPE production route need to
be investigated further to validate the proposed production route and financial viability. One area
of focus is the pilot scale up of equipment and the chemical reactions. Literature provides bench
top information on the reactions used in TPE production, but further testing must be conducted to
ensure scale-up of bench top reactions is appropriate. Reactor volumes may need to be modified
depending on conversion results from pilot testing of reactions.
Additionally, many of the nuances of the individual reactors will require scale up to test
the effectiveness of the proposed reactor design. The proposed PCl5 reactor atomization system
will need to be tested to ensure atomization of PCl3 is achievable. Bench top reactions require a
slow feed of PCl3 to increase contact area with chlorine gas. Atomization may not provide the
necessary surface area to mimic benchtop conversion. Testing must be conducted with the
atomizing gas to ensure no side products form. Secondary reactions could impact separation
systems, product purity and production rate.
The DPCM reactor condensation and heating systems will require scale up testing.
Literature information on the vapor condensation in the DPCM is limited, and the only provided
information is the presence of vacuum condensation. The shell and tube heat exchanger proposed
for condensation of the DPCM reactor vapor may not be adequate at large scale. Pilot testing
ensures reactor volumes are adequate and unintended pressure build up or product loss does not
occur within the DPCM reactor. Reactor design on the heating system for the DPCM to maintain
temperature at 220 C is also necessary. Insufficient heat supplied to the reactor may result in an
increase in residence times and decrease TPE production and potentially purity.
All heat exchangers in the proposed system must also be reevaluated to ensure the outlet
streams are at conditions presently specified. Initial sizing of most heat exchangers was
conducted using a shell and tube analysis, potentially leading to the oversizing of heat
exchangers. Lower heat exchanger outlet temperatures may require increases in heat supplied to
the distillation columns and to the endothermic reaction vessels. Testing on exchangers to check
for damage to Hastelloy C276 materials and to determine potential fouling effects must also be
extensively explored.
Separation system effectiveness must be scaled up and tested for the three different
systems. The outlet compositions of the distillation column and centrifuge are estimated with
ChemCad simulations. Magnetic drum product compositions are estimated from conversations
with Puritan Magnetics Inc. Further discussions with manufacturers, pilot testing, and quality
control analysis will be conducted to evaluate the effectiveness of separation.
Lastly material testing and alternate reaction pathways will be explored. Assuming the
proposed reaction pathway is used, testing construction materials resistance to chemical exposure
is necessary. To prevent and contain a catastrophic release, rigorous material testing must be
conducted to determine the impact of the chemicals used in this process upon the materials they
may be in contact with. Investigation for the presence of galvanic cells between dissimilar
materials will also be conducted to prevent unintentional corrosion of one material. Dielectric
materials placed at junctions will help reduce the corrosion risk. In conjunction with material
testing, alternate less environmentally hazardous reaction pathways will be investigated.
Reduction of hazardous chemicals used may decrease material costs, and make the process less
dangerous to the environment and people.
Process Narrative

Gaseous chlorine (Cl2) is delivered via railcar at 150 psia to a liquid atomization reactor,
but chlorine gas from a future process is recycled back as the primary source. Liquid phosphorus
trichloride (PCl3) is atomized with nitrogen gas and added to the reactor at an equimolar rate
with chlorine gas. Solid phosphorus pentachloride (PCl5) precipitates from the droplet and vapor
reactions and exits bottom of the reactor.
Solid PCl5 exits the reactor vessel and is transported via screw conveyor into a second
reactor, then mixed with benzophenone. The reactor vessel raises the temperature of the reactants
to 220oC. The PCl5 and benzophenone melt inside and react to form diphenyldichloromethane
(DPCM) and a byproduct of phosphorous oxychloride (POCl3) [1]. Reactant vapors formed
during this step are condensed to ensure no loss of reagents and ensure no hazardous material
may occur. Benzophenone and PCl5 are entirely consumed by this reaction and DPCM and
POCl3 exit in the reactor effluent.
The products are fed to a distillation column to separate the POCl3 and DPCM. The
overhead product from the distillation column contains POCl3 at purity greater than 99.99%. The
gaseous POCl3 is cooled in a concentric tube heat exchanger to 25oC where it can be collected.
The POCl3 will be sold as a byproduct. The bottoms product contains greater than 99% DPCM
which is fed to a concentric tube heat exchanger to reduce the temperature to 25oC and is fed into
an equilibrium reactor at 14.7 psia.
Nickel chloride powder dissolved in glyme is fed into the equilibrium reactor equimolar
to the DPCM and catalyzes the reaction [2]. Conversations with Dr. Mark Masthay and Dr.
Vladimir Benin [3] suggest chlorine gas as product of the reaction. Chlorine gas exits the reactor
and is recycled to the phosphorous pentachloride reaction vessel. The reaction yields solid TPE
which exits the reactor with trace amounts of DPCM and the nickel glyme complex. The TPE
and DPCM mixture is fed into a magnetic solids screen, also at 25C and 14.7 psia, where the
nickel glyme complex is recycled. TPE is separated from the DPCM by a centrifuge and DPCM
is recycled back to the equilibrium reactor. Solid TPE from the reactor effluent is packaged for
sale at a purity greater than 99.5%.
Stream 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Solids
PCl5 DCPM Bottoms, Distillate, POCl3, DCPM, Nickle Magnectic
Chlorine PCl3 Benzophenone TPE Reator Chlorine Separation DPCM
Description Reactor Reactor Distillation Distillation After Heat After Heat Complex Separation
Make Up Feed Feed Effluent Recycle Screen Recycle
Effluent Effluent Column Column Exchanger Exchanger Recycle Product
Out
Pressure (psia) 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7
Temperature (C) 25 25 50 25 220 305 105.8 25 25 25 25 25 25 25 25
Vapor Fraction 1 0 0 0 0.53 0 0 0 0 0 0 0 0 0 0
Liquid Fraction 0 1 1 1 0.47 1 1 1 1 1 1 1 1 1 1
Total Flow (kmol/h) Trace 6.22 6.22 6.22 12.45 6.22 6.22 6.22 6.22 6.28 9.46 6.22 3.17 3.11 0.06
Component Flow Rates
(kmol/h)
Cl2 Trace - - - - - - - - - - 6.22 - - -
PCl3 - 6.22 - - - - - - - - - - - - -
PCl5 - - 6.22 - - - - - - - - - - - -
Benzophenone - - - 6.22 - - - - - - - - - - -
DPCM - - - - 6.22 6.22 - - 6.22 - 0.06 - 0.06 - 0.06
Phosphorus(V) Oxychloride - - - - 6.22 - 6.22 6.22 - - - - - - -
Nickel-Glyme Complex - - - - - - - - - 6.28 6.28 - - - -
TPE - - - - - - - - - - 3.11 - 3.11 3.11 -
Bibliography

[1] E. Barnett, The preparation of organic compounds. London: J. & A. Churchill, 1920.
[2] S. Inaba, H. Matsumoto and R. Rieke, "Metallic nickel as a reagent for the coupling of
aromatic and benzylic halides", Tetrahedron Letters, vol. 23, no. 41, pp. 4215-4216, 1982.
[Accessed: October 20, 2017]
[3] M. Mastay and V. Benin, personal communication. March 2017